Detergent composition having enhanced anti-scaling efficacy

Abstract

A detergent composition and a method of using the composition are disclosed for providing effective cleaning and enhanced anti-scaling performance as compared to conventional detergent compositions. 【Solution means】The composition contains a scale-inhibiting organic phosphonate, an additional scale inhibitor including at least one polycarboxylate, polycarboxylic acid, or salts thereof, an alkali source, and an optional additional functional component.

Description

Technical Field

[0001] The present disclosure generally relates to detergent compositions and methods of using the compositions. Compositions containing a scale-inhibiting organic phosphonate, an additional scale inhibitor comprising at least one polycarboxylate, polycarboxylic acid, or a salt thereof, and an alkali source provide effective cleaning and enhanced anti-scaling performance compared to conventional detergent compositions.

Background Art

[0002] The development of detergent compositions with higher alkalinity while also improving anti-scaling performance remains a commercially unmet need. High-alkalinity concentrated detergents used with water having various hardness levels can have detrimental effects in many systems. For example, when hard water contacts a surface either alone or in combination with a detergent composition, it may cause the precipitation of hard water scale on the contacted surface. Scaling is the precipitation of salts from a solution that is supersaturated with respect to the salts. Generally, hard water refers to water having a total level of calcium and magnesium ions greater than about 100 ppm when expressed in ppm of calcium carbonate.

[0003] Hard water is known to reduce the effectiveness of conventional alkaline detergents. Detergents contain chelating agents or sequestering agents that are intended to be mixed with hard water in an amount sufficient to address the hardness and also prevent scaling. However, in many cases, the hardness of the water exceeds the chelating ability of the composition. As a result, free calcium ions can become available to cause precipitation or attack the active ingredients of the composition, leading to other detrimental effects such as insufficient cleaning effectiveness or the accumulation of lime scale. Therefore, improvement in anti-scaling performance is still highly needed.

[0004] Scaling significantly interferes with cleaning. Particularly in areas with high water hardness, the problem of scaling can present a very serious challenge. For example, scale removal steps such as treatment by acid cleaning may be required. A reduction in the frequency of scale removal results in savings in labor time and labor costs, transportation costs, and energy. Summary of the Invention Problems to be Solved by the Invention

[0005] Accordingly, an object of the present disclosure is to provide a detergent composition that provides desirable cleaning and improved anti-scaling performance.

[0006] A further object of the present disclosure is to provide a detergent composition that can make the accumulation of scale more gradual, and thus requires less frequent (or no) scale removal interventions.

[0007] Another object of the present disclosure is to formulate a detergent composition that provides improved customer acceptability through use.

[0008] Other objects, embodiments, and advantages of the present disclosure will be apparent to those skilled in the art upon consideration of the following disclosure, drawings, and appended claims. Means for Solving the Problems

[0009] The following objects, features, advantages, aspects, and / or embodiments are not exhaustive and do not limit the entire disclosure. A single embodiment need not provide every object, feature, or advantage. Any of the objects, features, advantages, aspects, and / or embodiments disclosed herein can be fully or partially integrated with each other.

[0010] The main objective, features, and / or advantages of the present disclosure include improving or overcoming the deficiencies in the art and commercially available products by providing enhanced detergency and anti-scaling performance as compared to alkaline detergent compositions containing conventional chelating agents and builders.

[0011] According to some aspects of the present disclosure, the detergent composition has the following structure:

Chemical formula

Chemical formula

Chemical formula

[0012] According to an additional aspect of the present disclosure, a method of using the detergent composition includes providing the detergent composition described herein, contacting the detergent composition with water to form a use solution, and contacting the use solution with a surface in need of cleaning and anti-scaling.

[0013] These and / or other objectives, features, advantages, aspects, and / or embodiments will become apparent to those skilled in the art after considering the following brief description of the drawings and the detailed description. Furthermore, the present disclosure includes, at least, (a) combinations of the disclosed aspects and / or embodiments, and / or (b) reasonable modifications that are not shown or described, aspects and / or embodiments that are not explicitly disclosed but can be understood by reading the present disclosure.

[0014] Although multiple embodiments are disclosed, further additional embodiments will become apparent to those skilled in the art from the following detailed description that illustrates and describes exemplary embodiments. Therefore, the drawings and the detailed description should be considered to be essentially exemplary and not restrictive.

Brief Description of the Drawings

[0015]

Figure 1

[0016]

Figure 2A

Figure 2B

Figure 2C

[0017] Various embodiments of the present disclosure will be described in detail with reference to the drawings, and like reference numerals represent like components throughout several figures. References to various embodiments do not limit the scope of the present disclosure. The figures presented herein are not limitations to various embodiments according to the present disclosure but are presented for illustrative explanation of the present invention. For the ease of understanding the present invention, those skilled in the art do not need to consider almost countless different permutations of the features described in the following detailed description within the detached drawings.

Modes for Carrying Out the Invention

[0018] The present disclosure should not be limited to what is described herein and can be modified and understood by those skilled in the art. Unless otherwise specified, the features shown or described are not essential to enable the basic operations of the present disclosure. Surprisingly, it has been found that the described detergent compositions have enhanced synergistic anti-scaling performance compared to conventional chelating agents and threshold inhibitors used in detergent compositions.

[0019] Furthermore, it should be understood that all technical terms used herein are for the sole purpose of describing particular embodiments and are not intended to limit in any way or scope. For example, as used in this specification and the appended claims, the singular forms "a", "an", and "the" may include the plural referents unless the context clearly dictates otherwise. Further, all units, prefixes, and symbols may be expressed in their SI-approved form.

[0020] The numerical ranges recited herein include the numbers defining the range and include each integer within the defined range. Throughout the present disclosure, various aspects of the present disclosure are presented in a range format. The description in range format is merely for convenience and brevity and should not be construed as an immutable limitation on the scope of the present disclosure. Accordingly, the recitation of a range should be considered to specifically disclose all possible sub-ranges, fractions, and individual numerical values within that range. For example, a range description such as 1 to 6 should be considered to specifically disclose not only sub-ranges such as 1 to 3, 1 to 4, 1 to 5, 2 to 4, 2 to 6, 3 to 6, etc., but also the individual numbers within that range, such as 1, 2, 3, 4, 5, and 6, as well as decimals and fractions, such as 1.2, 3.8, 1 and 1 / 2, and 4 and 3 / 4. This applies regardless of the width of the range.

[0021] As used herein, the term "and / or", e.g., "X and / or Y", is to be understood to mean either "X and Y" or "X or Y", and is to be construed as providing explicit support for both meanings or either meaning, e.g., A and / or B includes the options i) A, ii) B, or iii) A and B.

[0022] For clarity, it should be understood that certain features described herein in the context of separate embodiments may be provided in combination in a single embodiment. Conversely, for brevity, various features described in the context of a single embodiment may be provided separately or in any sub-combination.

[0023] The methods and compositions of the present disclosure may include, consist essentially of, or consist of the components and ingredients of the present disclosure and other ingredients described herein. As used herein, "consisting essentially of" means that a method, system, apparatus, and composition may include additional steps, components, or ingredients, but only to the extent that the additional steps, components, or ingredients do not substantially change the basic and novel characteristics of the claimed method, system, apparatus, and composition.

[0024] Unless otherwise defined, all technical and scientific terms used above have the same meaning as commonly understood by one of ordinary skill in the art relevant to the embodiments of the present disclosure.

[0025] The terms "invention" or "the invention" are not intended to refer to any single embodiment of a particular invention, but rather are intended to encompass all possible embodiments described in the specification and claims.

[0026] As used herein, the term "about" refers to variations in quantities that can occur by typical measurement techniques and equipment for any quantifiable variable, including but not limited to mass, volume, time, temperature, pH, etc. Further, considering the handling procedures of solids and liquids used in the real world, there are likely to be certain inadvertent errors and variations due to differences in the manufacture, source, or purity of the components used to make a composition or carry out a method, etc. The term "about" also encompasses these variations. Whether or not modified by the term "about", the claims include equivalents to that amount.

[0027] The terms "actives" or "percent actives" or "percent by weight actives" or "actives concentration" are used interchangeably herein and refer to the concentration expressed as a percentage of the components involved in washing, minus the inert components such as water or salts. For example, it may be indicated by a percentage in parentheses, such as "chemical (10%)".

[0028] As used herein, the term "alkyl" or "alkyl group" refers to a saturated hydrocarbon having one or more carbon atoms, including straight-chain alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.), cyclic alkyl groups (or "cycloalkyl" or "alicyclic" or "carbocyclic" groups) (e.g., cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.), branched-chain alkyl groups (e.g., isopropyl, tert-butyl, sec-butyl, isobutyl, etc.), and alkyl-substituted alkyl groups (e.g., alkyl-substituted cycloalkyl groups and cycloalkyl-substituted alkyl groups).

[0029] Unless otherwise defined, the term "alkyl" includes both "unsubstituted alkyl" and "substituted alkyl". As used herein, the term "substituted alkyl" refers to an alkyl group having a substituent that replaces one or more hydrogens on one or more carbons of the hydrocarbon backbone. Such substituents include, for example, alkenyl, alkynyl, halogeno, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonato, phosphinato, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl, and ureido), imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfate, alkylsulfinyl, sulfonate, sulfamoyl, sulfonamide, nitro, trifluoromethyl, cyano, azide, heterocyclic, alkylaryl, or aromatic (including heteroaromatic) groups.

[0030] In some embodiments, substituted alkyl can include a heterocyclic group. As used herein, the term "heterocyclic group" includes a closed-ring structure similar to a carbocyclic group in which one or more of the carbon atoms in the ring are elements other than carbon, such as nitrogen, sulfur, or oxygen. The heterocyclic group can be saturated or unsaturated. Exemplary heterocyclic groups include, but are not limited to, aziridine, ethylene oxide (epoxide, oxirane), thiirane (episulfide), dioxolane, azetidine, oxetane, thietane, dioxetane, dithietane, dithieto, azolidine, pyrrolidine, pyrroline, oxolane, dihydrofuran, and furan.

[0031] The term "configured" describes a structure that is capable of performing a task or adopting a particular configuration. The term "configured" can be used interchangeably with other similar terms such as constructed, arranged, adapted, manufactured, etc.

[0032] Terms characterizing order, position, and / or orientation are not limiting and are only referenced according to the presented figures.

[0033] As used herein, the term "exemplary" refers to an example, instance, or illustration and does not indicate the most preferred embodiment unless otherwise specified.

[0034] As used herein, the phrase "food processing surface" refers to the surfaces of utensils, machines, equipment, structures, buildings, etc. that are used as part of food processing, cooking, or storage activities. Examples of food processing surfaces include the surfaces of food processing or cooking equipment (e.g., slicing equipment, canning equipment, or conveying equipment including waterways), food processing utensils (e.g., utensils, tableware, wash ware, and bar glass surfaces), and the floors, walls, or fixture surfaces of structures where food processing is performed. Food processing surfaces are found and used in food spoilage prevention air circulation systems, aseptic packaging disinfection, food refrigeration and cooler cleaning agents and disinfectants, warewashing disinfection, bleach washing and disinfection, food packaging materials, cutting board additives, third-sink disinfection, beverage coolers and warmers, water for meat cooling or hot water treatment, automatic tableware disinfectants, disinfectant gels, cooling towers, antimicrobial clothing sprays for food processing, and non-aqueous to low-aqueous food cooking lubricants, oils, and rinse additives.

[0035] As used herein, the term "free of" means that the composition either completely lacks the constituent or has a small amount of the constituent that does not affect the performance of the composition. The component may be present as an impurity or an extraneous substance and is considered to be less than about 0.1% by weight, and in yet another embodiment, the amount of the component is less than about 0.01% by weight, or 0% by weight.

[0036] The term "generally" encompasses both "about" and "substantially".

[0037] The term "hard surface" refers to a solid and substantially non-flexible surface such as countertops, tiles, floors, walls, panels, windows, sanitary ware, kitchen and bathroom appliances, electrical appliances, engines, circuit boards, dishes, mirrors, windows, monitors, touchscreens, and thermostats. The hard surface is not limited by the material, and for example, the hard surface can be glass, metal, tile, vinyl, linoleum, composite materials, wood, plastic, etc. The hard surface can include, for example, healthcare surfaces and food processing surfaces.

[0038] As used herein, the term "instrument" refers to various medical or dental instruments or devices that can benefit from cleaning with the compositions described herein. As used herein, the phrases "medical instrument", "dental instrument", "medical device", "dental device", "medical equipment", or "dental equipment" refer to instruments, devices, tools, electrical appliances, apparatuses, and equipment used in medicine or dentistry. Such instruments, devices, and facilities are sterilized at low temperature, immersed, or washed and then heat-sterilized, or can benefit from purification in the compositions of the present disclosure. These various instruments, devices, and equipment include, but are not limited to, diagnostic instruments, trays, pans, holders, racks, forceps, scissors, shears, saws (e.g., bone saws and their blades), hemostatic forceps, knives, scalpels, bone forceps, files, nippers, drills, drill bits, rasps, burs, spreaders, breakers, elevators, clamps, needle holders, carriers, clips, hooks, osteotomes, curettes, explorers, retractors, straighteners, perforating forceps, extractors, spatulas, corneal incisors, spatulas, expressors, trocars, dilators, cages, glassware, tubing, catheters, cannulas, plugs, stents, scopes (e.g., endoscopes, stethoscopes, and arthroscopes), and related equipment, etc., or combinations thereof.

[0039] As used herein, the term "polymer" refers to a molecular complex composed of more than 10 monomer units, and generally includes, but is not limited to, homopolymers, copolymers such as block, graft, random, and alternating copolymers, terpolymers, and higher-order "x"-mers, and further includes their analogs, derivatives, combinations, and blends thereof. Further, unless specifically limited otherwise, the term "polymer" is intended to include all possible isomeric structures of the molecules, including, but not limited to, isotactic, syndiotactic, and random symmetries, and combinations thereof. Further, unless specifically limited otherwise, the term "polymer" is intended to include all possible geometric structures of the molecules.

[0040] As used herein, the term "soil" or "stain" refers to any soil, including but not limited to non-polar oily and / or hydrophobic substances, which may or may not include particulate matter such as industrial soils, inorganic clays, sands, natural mineral substances, carbon black, graphite, kaolin, environmental dusts, and / or food-based soils such as blood, proteinaceous soils, starch soils, fatty soils, and cellulosic soils.

[0041] The "scope" of the present disclosure is defined by the appended claims, along with the full scope of equivalents to which such claims are entitled. The scope of the present disclosure is further considered to include any possible modifications to any of the aspects and / or embodiments disclosed herein that would result in other embodiments, combinations, sub-combinations, etc., that would be apparent to those skilled in the art.

[0042] The term "substantially" refers to a large or significant degree. Thus, "substantially" can refer to a plurality, majority, and / or overwhelming majority of the quantifiable variables, given the appropriate context.

[0043] The term "surfactant" or "surface active agent" refers to an organic chemical substance that, when added to a liquid, changes the properties of that liquid at the surface.

[0044] As used herein, the term "article" refers to items such as food and cooking utensils, tableware, and other hard surfaces such as showers, sinks, toilets, bathtubs, countertops, windows, mirrors, transport vehicles, and floors. As used herein, the term "article cleaning" refers to cleaning, purifying, or rinsing an article. Articles also refer to plastic items. Examples of plastics that can be cleaned with this composition include, but are not limited to, polypropylene polymer (PP), polycarbonate polymer (PC), melamine formaldehyde resin or melamine resin (melamine), acrylonitrile-butadiene-styrene polymer (ABS), and polysulfone polymer (PS). Other exemplary plastics that can be cleaned using the compounds and compositions of the present disclosure include polyethylene terephthalate (PET), polystyrene, and polyamide.

[0045] The terms "weight percent", "wt-%", "percent by weight", "% by weight", and variations thereof, as used herein, refer to the concentration of a substance obtained by dividing the weight of the substance by the total weight of the composition and multiplying by 100. It is understood that as used herein, terms such as "percent", "%", etc. are intended to be synonymous with "weight percent", "wt-%", etc.

[0046] Detergent composition

[0047] According to an embodiment, the detergent composition comprises an organic phosphonate, an additional scale inhibitor which is a polycarboxylate, a polycarboxylic acid, or a salt thereof, an alkali source, and water. The detergent composition can include additional functional components and can be provided as a concentrate or a use composition. Exemplary compositions are shown in Tables 1A (solid) and 1B (liquid) in weight percent. The components can have 100% active ingredient percent, but it should be noted that Tables 1A - 1B list the total weight percent of the raw materials (i.e., active ingredient concentration + inert ingredient), rather than the active ingredient percent of the components.

[0048] [Table 1]

[0049] [Table 2]

[0050] Solid composition The detergent composition is preferably a solid composition. Solid detergent compositions include various forms such as solids, pellets, blocks, tablets, and powders. By way of example, the pellets can have a diameter of about 1 mm to about 10 mm, the tablets can have a diameter of about 1 mm to about 10 mm or about 1 cm to about 10 cm, and the blocks can have a diameter of at least about 10 cm. It should be understood that the term "solid" refers to the state of the composition under the expected storage and use conditions of the solid cleaning composition. Generally, when provided at a temperature of up to about 100°F or less than about 120°F, the detergent composition is expected to remain solid.

[0051] In certain embodiments, the solid cleaning composition is provided in unit dose form. A unit dose refers to a unit of the solid cleaning composition sized such that the entire unit is used during one cycle, for example, one wash cycle of a dishwashing machine. When the solid cleaning composition is provided as a unit dose, it can have a mass of from about 1 g to about 50 g. In other embodiments, the composition can be a solid, pellet, or tablet having a size of from about 50 g to 250 g, from about 100 g or more, or from about 40 g to about 11,000 g.

[0052] In other embodiments, the solid cleaning composition is provided in the form of a multi-use solid such as a block or multiple pellets and can be repeatedly used to produce an aqueous cleaning composition for multiple wash cycles. In certain embodiments, the solid cleaning composition is provided as a solid having a mass of from about 5 g to about 10 kg. In certain embodiments, the multi-use solid cleaning composition has a mass of from about 1 to about 10 kg. In further embodiments, the multi-use solid cleaning composition has a mass of from about 5 kg to about 8 kg. In other embodiments, the multi-use solid cleaning composition has a mass of from about 5 g to about 1 kg or from about 5 g to about 500 g.

[0053] In embodiments, the solid is a cast, compressed, or extruded solid. The components can be mixed, extruded, or cast to form a solid such as a pellet, powder, or block. Heat can be applied from an external source to facilitate processing of the mixture.

[0054] Liquid composition The detergent composition can also include a liquid composition. Any form of liquid composition including a concentrated composition can be provided.

[0055] Organic phosphonate The detergent composition contains an organic phosphonate. The organic phosphonate is an organic derivative of phosphonic acid, HP(O)(OH)2. Unlike conventional organic phosphonate scale inhibitors such as 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) or 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC), the organic phosphonate contains a single C-N bond adjacent (proximate) to the C-P bond.

[0056] The organic phosphonate has the following general structure:

Chemical formula

Chemical formula

Chemical formula

[0057] In Structures I - V, the salt form of Y or Y' is preferably a suitable cation such as sodium or potassium.

[0058] The described organic phosphonate is particularly suitable for use in preventing scaling in utensil cleaning applications including detergent use.

[0059] Preferred classes of organic phosphonates include polyaminopolyether methylene phosphonic acid and polyether phosphonic acids containing polyaminopolyether methylene phosphonate, for example, the following structure:

Chemical formula

Chemical formula

[0060] Further exemplary organic phosphonates include the following structures:

Chemical formula

[0061] Even further exemplary organic phosphonates include HMDTMP ((HO)2P(O)CH2)2N(CH2)6N(CH22P(O)(OH)2)2) having the following structure:

Chemical formula

[0062] Even further exemplary organic phosphonates include DTMPA ((HO)2P(O)CH2N[CH2CH2N(CH2P(O)(OH)2)2]2) having the following structure:

Chemical formula

[0063] Even more preferred classes of organic phosphonates include alkylene oxide phosphonates. Any combination of the aforementioned scale inhibitors can be used, and salts of any of these compounds, such as ammonium salts, can also be used. In some embodiments, the aforementioned scale inhibitors can be further combined with conventional phosphonates. Examples of phosphonates include phosphinobutanetricarboxylic acid oligomers (PSO) described in U.S. Patent No. 8,871,699, 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC), 1-hydroxyethane-1,1-diphosphonic acid, HEDP, aminotri(methylenephosphonic acid); 2-hydroxyethyliminobis(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonate), sodium salt (DTPMP), hexamethylenediamine(tetramethylenephosphonate), potassium salt bis(hexamethylene)triamine(pentamethylenephosphonic acid); and phosphorous acid, but are not limited thereto.

[0064] In some embodiments, the organic phosphonate is included in the solid detergent composition in an amount of at least about 1 wt% to about 30 wt%, about 1 wt% to about 25 wt%, about 1 wt% to about 20 wt%, about 1 wt% to about 15 wt%, about 1 wt% to about 10 wt%, or about 1 wt% to about 8 wt%. Additionally, without limitation according to the present disclosure, all recited ranges include the numbers defining the range and each integer within the defined range.

[0065] In some embodiments, the organic phosphonate is included in the liquid detergent composition in an amount of at least about 1 wt% to about 30 wt%, about 1 wt% to about 25 wt%, about 1 wt% to about 20 wt%, about 1 wt% to about 15 wt%, about 1 wt% to about 10 wt%, or about 1 wt% to about 8 wt%. Additionally, without limitation according to the present disclosure, all recited ranges include the numbers defining the range and each integer within the defined range.

[0066] As described herein, the organic phosphonates according to the formulas and various structures disclosed herein are phosphonates or their salts (including cations). In a preferred embodiment, the organic phosphonate does not contain any betaine structure or polybetaine structure such that a charge-separated neutral molecule is present.

[0067] In some embodiments, the organic phosphonate does not contain ATMP (aminotris(methylenephosphonic acid) having the chemical formula N(CH2PO3H2)3). In still further embodiments, the organic phosphonate does not contain PBTC (2-phosphonobutane-1,2,4-tricarboxylic acid).

[0068] Additional scale inhibitor The detergent composition includes at least one additional scale inhibitor including a polycarboxylate, a polycarboxylic acid, or a salt thereof. Advantageously, the combination of the organic phosphonate and the polycarboxylate, polycarboxylic acid, or a salt thereof provides a synergistic improvement in scale prevention that exceeds that of conventional scale prevention or threshold inhibitors used for scale prevention and hard water treatment in detergent compositions.

[0069] Exemplary polycarboxylates that can be used as scale inhibitors include those having pendant carboxylate (--CO2--) groups such as polyacrylic acid, maleic acid, maleic acid / olefin copolymer, sulfonated copolymer or terpolymer, acrylic acid / maleic acid copolymer, polymethacrylic acid, acrylic acid-methacrylic acid copolymer, hydrolyzed polyacrylamide, hydrolyzed polymethacrylamide, hydrolyzed polyamide-methacrylamide copolymer, hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile, and hydrolyzed acrylonitrile-methacrylonitrile copolymer, but are not limited thereto.

[0070] Examples of suitable additional polymers include homopolymers of polyacrylic acid, polymethacrylic acid, and polymaleic acid, and copolymers of acrylic acid, methacrylic acid, or maleic acid (and combinations thereof).

[0071] Preferred groups of polycarboxylates include polycarboxylic acid polymers (e.g., Acusol polymers) including polyacrylic acid homopolymers and polymaleic acid homopolymers, and polymers modified with fatty acid end groups. Exemplary polyacrylic acid homopolymers include those having a molecular weight of about 500 to 100,000 g / mol, or about 1,000 to 50,000 g / mol, or about 1,000 to 25,000 g / mol.

[0072] A variety of such polycarboxylate homopolymers, copolymers, and terpolymers are known, described in patents and other literature, and are commercially available. Exemplary polycarboxylates that can be used include, for example, polyacrylates; polymethacrylates; homopolymers, copolymers, and terpolymers of polymaleates. Examples of suitable polymers include acrylic acid homopolymers, maleic acid homopolymers, methacrylic acid homopolymers, acrylic / maleic copolymers, maleic (maelic) copolymers, acrylic / methacrylic copolymers, maleic acid terpolymers, hydrophobically modified acrylic acid copolymers and terpolymers, hydrophobically modified maleic acid copolymers and terpolymers, and hydrophobically modified methacrylic acid copolymers and terpolymers. Suitable polymers preferably have a molecular weight of about 500 to about 50,000 g / mol, more preferably about 500 to about 25,000 g / mol, and particularly about 500 to about 10,000 g / mol.

[0073] More suitable polycarboxylic acids are acyclic, alicyclic, heterocyclic, and aromatic carboxylic acids, in which case they preferably contain at least two carboxyl groups separated from each other by two or fewer carbon atoms in each case. Examples of polycarboxylates containing two carboxyl groups include water-soluble salts of malonic acid, (ethylenedioxy)diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid, and fumaric acid. Polycarboxylates containing three carboxyl groups include, for example, water-soluble citrate salts. Correspondingly, a suitable hydroxycarboxylic acid is, for example, citric acid. Another suitable polycarboxylic acid is a homopolymer of acrylic acid. The polycarboxylate can be further end-capped with a sulfonate.

[0074] In some embodiments, the detergent composition includes more than one additional scale inhibitor including a polycarboxylate, a polycarboxylic acid, or a salt thereof. In some embodiments, the detergent composition includes two additional scale inhibitors including a polycarboxylate, a polycarboxylic acid, or a salt thereof. In a more preferred embodiment, the detergent composition includes polyacrylic acid and polymaleic acid.

[0075] In some embodiments, the additional scale inhibitor is included in the solid detergent composition in an amount of at least about 0 wt% to about 20 wt%, about 1 wt% to about 20 wt%, about 1 wt% to about 15 wt%, about 1 wt% to about 10 wt%, about 1 wt% to about 8 wt%, or about 2 wt% to about 8 wt%. Additionally, without limitation according to the present disclosure, all recited ranges include the numbers defining the range and each integer within the defined range.

[0076] In some embodiments, the additional scale inhibitor is included in the solid detergent composition in an amount of at least about 0 wt% to about 20 wt%, about 1 wt% to about 20 wt%, about 1 wt% to about 15 wt%, about 1 wt% to about 10 wt%, about 1 wt% to about 8 wt%, or about 1 wt% to about 6 wt%. Additionally, without limitation according to the present disclosure, all recited ranges include the numbers defining the range and each integer within the defined range.

[0077] In embodiments, the detergent composition does not contain a carboxylic acid terpolymer.

[0078] Alkali source The detergent composition includes one or more alkali sources. The alkali source can be any alkali source compatible with the other components of the detergent composition. In embodiments, the alkali source includes an alkali metal hydroxide. Preferred alkali sources include alkali metal hydroxides including sodium hydroxide, potassium hydroxide, and lithium hydroxide, or mixtures thereof, and most preferably sodium hydroxide and / or potassium hydroxide.

[0079] Additional alkali sources that can be combined with the alkali metal hydroxide include alkali metal carbonates, alkali metal silicates, alkali metal salts, phosphates, amines, and mixtures thereof. In some embodiments, the alkali metal hydroxide alkali source is combined with a second alkali source including an alkali metal carbonate.

[0080] In some embodiments, the alkali source is included in the solid detergent composition in an amount of at least about 10 wt% to about 90 wt%, or about 10 wt% to about 80 wt%, about 20 wt% to about 80 wt%, about 30 wt% to about 80 wt%, about 40 wt% to about 80 wt%, or about 50 wt% to about 80 wt%. In some embodiments for the solid composition, the total amount of the alkali source relative to (alkali source + water) is about 60 - 80% (e.g., alkali / (water + alkali)), and the solid maintains stability. Additionally, without limitation according to the present disclosure, all recited ranges include the numbers defining the range and each integer within the defined range.

[0081] In some embodiments, the alkali source is included in the liquid detergent composition in an amount of at least about 5 wt% to about 80 wt%, about 10 wt% to about 70 wt%, about 10 wt% to about 60 wt%, about 10 wt% to about 50 wt%, or about 10 wt% to about 40 wt%. Additionally, without limitation according to the present disclosure, all recited ranges include the numbers defining the range and each integer within the defined range.

[0082] Water The detergent composition can contain varying amounts of water depending on the technology for treating the solid composition. Water provides a medium for dissolving, suspending, or carrying other components of the composition. Water can also function to deliver the composition to the object and wet it.

[0083] In some embodiments, water constitutes the remainder of the detergent composition, excluding scale - inhibiting organic phosphonates, additional scale inhibitors, the alkali source, and any additional functional components. The amount and type of water depend particularly on the nature of the overall composition, environmental storage, and method of application including concentrated compositions, the form of the composition, and the intended delivery method. In particular, the carrier should be selected and used at a concentration that does not inhibit the efficacy of the functional components in the composition for the intended use, e.g., bleaching, disinfection, cleaning.

[0084] In certain embodiments, the solid detergent composition comprises from about 1% to about 30% by weight of water, from about 5% to about 30% by weight of water, or from about 10% to about 30% by weight of water. It is understood that all of the values and ranges between these values are encompassed by the present invention.

[0085] In certain embodiments, the liquid detergent composition comprises from about 30% to about 90% by weight of water, from about 40% to about 90% by weight of water, or from about 50% to about 90% by weight of water. It is understood that all of the values and ranges between these values are encompassed by the present invention.

[0086] Additional functional components The components of the detergent composition can be further combined with various functional components suitable for the uses disclosed herein. In some embodiments, a detergent composition comprising a scale-inhibiting organic phosphonate, an additional scale inhibitor comprising at least one polycarboxylate, polycarboxylic acid, or salts thereof, and an alkali source constitutes a majority or substantially all of the total weight of the composition. In other embodiments, a detergent composition comprising a scale-inhibiting organic phosphonate, an additional scale inhibitor comprising at least one polycarboxylate, polycarboxylic acid, or salts thereof, an alkali source, and / or at least one additional functional component constitutes a majority or substantially all of the total weight of the composition. For example, in some embodiments, the additional functional component is present in little or no amount in the composition.

[0087] In other embodiments, additional functional components may be included in the detergent composition. The functional components provide the desired properties and functionality to the composition. For the purposes of this application, the term "functional component" includes materials that, when dispersed or dissolved in a use solution such as an aqueous solution and / or a concentrate solution, provide beneficial properties in a particular use. Some specific examples of functional materials are considered in more detail below, but the specific materials considered are given merely as examples and a wide variety of other functional components may be used. For example, many of the functional materials considered below relate to materials used in cleaning. However, other embodiments may include functional components for use in other applications.

[0088] In some embodiments, the detergent composition may include optical brighteners, defoamers, anti-redeposition agents, bleaching agents, solubility modifiers, dispersants, metal protectants, stabilizers, hardeners, fillers, preservatives, corrosion inhibitors, builders / metal ion sequestering agents / chelating agents, enzymes, aesthetic enhancers including fragrances and / or dyes, additional rheology and / or solubility modifiers or thickeners, hydrotropes or couplers, buffers, solvents, additional detergents including surfactants, etc.

[0089] In other embodiments, additional detergents may be included in the detergent composition. In some embodiments, the detergent composition and the additional detergents do not include alkanolamines containing ethanolamine and / or taurine. In further embodiments, the detergent composition does not include polyethylene glycol. In further embodiments, the detergent composition and the additional detergents do not include surfactants and do not include alcohol alkoxylates containing alcohol ethoxylates and polyoxyethylene ethers of alcohol ethoxylates.

[0090] According to embodiments of the present disclosure, various additional functional components may be provided in the composition in an amount of about 0 wt% to about 30 wt%, about 0 wt% to about 25 wt%, about 0 wt% to about 20 wt%, about 0.01 wt% to about 30 wt%, about 0.1 wt% to about 30 wt%, about 1 wt% to about 30 wt%, about 1 wt% to about 25 wt%, about 1 wt% to about 20 wt%, or about 1 wt% to about 15 wt%. Additionally, without limitation according to the present disclosure, all recited ranges include the numbers defining the range and include each integer within the defined range.

[0091] Detergent builder The components of the detergent composition may be further combined with a non-phosphonate builder. Various components may contain trace amounts of phosphorus, but carboxylates such as citrate, tartrate, or gluconate are also suitable. Useful aminocarboxylic acid materials containing little or no NTA include N-hydroxyethyliminodiacetic acid, ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylethylenediaminetriacetic acid, and methylglycinediacetic acid (MGDA), glutamic acid-diacetic acid (GLDA), iminodisuccinic acid (IDA), hydroxyiminodisuccinic acid, ethylenediaminedisuccinic acid (EDDS), aspartic acid-diacetic acid, and their salts, but are not limited thereto. Particularly preferred builders are MGDA and GLDA and their salts, and / or other similar acids having an amino group with a carboxylic acid substituent.

[0092] The components of the detergent composition may be further combined with an additional phosphonate builder containing a conventional organic phosphonate scale inhibitor such as 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) or 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC).

[0093] In one aspect, exemplary builders are selected from the group consisting of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, and methylglycine diacetic acid, glutamic acid diacetic acid, iminodisuccinic acid, hydroxyiminodisuccinic acid, ethylenediaminedisuccinic acid, aspartic acid diacetic acid, and salts thereof. Particularly preferred builders are methylglycine diacetic acid and salts thereof.

[0094] According to embodiments of the present disclosure, additional builder can be provided in the composition in an amount of from about 0 wt% to about 30 wt%, from about 0 wt% to about 25 wt%, from about 0 wt% to about 20 wt%, from about 0.01 wt% to about 30 wt%, from about 0.1 wt% to about 30 wt%, from about 1 wt% to about 30 wt%, from about 1 wt% to about 25 wt%, from about 1 wt% to about 20 wt%, or from about 1 wt% to about 15 wt%. Additionally, without limitation according to the present disclosure, all recited ranges include the numbers defining the range and include each integer within the defined range.

[0095] Method of Use

[0096] The method of using the detergent composition is particularly suitable for consumer or commercial dishwashing. The method can include first contacting the detergent composition with water to form a use solution of the detergent composition, which can be provided as a liquid concentrate or a solid composition. Advantageously, the concentrate or use solution of the composition provides cleaning efficacy and anti-scaling efficacy on various surfaces that require cleaning. These methods overcome the limitations of detergent compositions that provide inadequate anti-scaling, including the common scaling problems in various applications where hard water sources are used in the cleaning and / or rinsing processes.

[0097] The detergent composition is particularly suitable for use in alkaline detergent applications where prevention of the accumulation of hard water scale on surfaces is desired. Additionally, the method is well-suited for controlling the increase in water hardness on multiple surfaces. The method prevents the accumulation of moderate to severe hardness on the treated substrate surface, which advantageously improves the aesthetic appearance of the surface. In certain embodiments, surfaces that require prevention of hard water scale accumulation include, for example, plastic, metal, and / or glass surfaces.

[0098] The detergent composition is particularly suitable for treating the surfaces of utensils, appliances, and the like, as well as various electrical appliance surfaces such as kitchen or food processing surfaces. These utensil and electrical appliance surfaces can each be made from a variety of materials. Advantageously, the method provides effective cleaning (i.e., detergency) and scale removal. In embodiments, using a detergent containing a scale-inhibiting organic phosphonate reduces the need for a supplemental scale removal step as the composition provides effective anti-scaling. As a result, the method of use reduces the need for an acid rinse step and / or a descaling step (i.e., a separate cleaning cycle using strong acid to clean the machine) to remove films or residues on the treated surface that accumulate over time. These advantages are achieved while providing at least substantially similar or improved cleaning and anti-scaling.

[0099] In embodiments, the method of using the detergent composition significantly reduces the need to use a scale removal step in a dishwasher. In embodiments, the use of a multi-purpose liquid rinse aid composition provides a rinsing efficacy that further avoids the need for scale removal from the machine for at least about 1,000 hours of machine operation, at least about 1,100 hours of machine operation, at least about 1,200 hours of machine operation, at least about 1,300 hours of machine operation, or at least about 1,400 hours of machine operation.

[0100] In a further embodiment, the method of using the detergent composition significantly reduces the need to use a scale removal step in the rinse cylinder. In an embodiment, the use of the detergent composition provides a scale prevention efficacy that further avoids the need for scale removal in the rinse cylinder for at least about 4 months, at least about 5 months, or at least about 6 months.

[0101] Without being limited to a particular mechanism of action, the organic phosphonate, which is an alkylene oxide phosphonate, adds hydrophilicity with an ethylene oxide group and has high solubility and calcium resistance, thus providing benefits under hard water conditions where scaling is harmful to various surfaces and electrical equipment. Further, a synergistic combination of scale prevention is achieved by combining the organic phosphonate with a polycarboxylate polymer that provides further physical separation or dispersion effects.

[0102] Exemplary disclosures of dishwashing applications are described in U.S. Patent Nos. 8,758,520, 9,139,800, and 10,905,305. The method can be performed in any consumer or commercial dishwashing machine, including, for example, those described in U.S. Patent No. 8,092,613, the entire contents of which, including all figures and drawings, are incorporated herein by reference. Some non-limiting examples of dishwashing machines include door-type or hood-type machines, conveyor-type machines, undercounter machines, glass washers, flight-type machines, machines for pots and pans, utensil washers, and domestic dishwashing machines. The dishwashing machine can be either a single-tank or multi-tank washing machine.

[0103] A door-type dishwasher, also referred to as a hood-type dishwasher, refers to a commercial dishwasher that places soiled dishes on a rack and then moves the rack into the dishwasher. The door-type dishwasher washes one or two racks at a time. In such a machine, the rack is stationary and the washing and rinsing arms move. The door-type machine includes two sets of arms: a set of washing arms and one rinsing arm or a set of rinsing arms. The door-type machine may be a high-temperature machine or a low-temperature machine. In a high-temperature machine, the dishes are sanitized by hot water. In a low-temperature machine, the dishes are sanitized by a chemical detergent. The door-type machine can be either a recirculating machine or a dump and fill machine. In a recirculating machine, the detergent solution is reused or "recirculated" between wash cycles. The concentration of the detergent solution is adjusted between wash cycles to maintain an appropriate concentration. In a dump and fill machine, the wash solution is not reused between wash cycles. A new detergent solution is added before the next wash cycle.

[0104] In addition to cleaning utensils, the detergent composition is suitable for cleaning various additional surfaces to provide cleaning and scale removal. The ability to treat other surfaces such as electrical equipment and surfaces that are prone to scaling because they come into contact with hard water provides benefits to the detergent composition.

[0105] In embodiments using the detergent composition, the composition may be contacted with or mixed with a water source, preferably water, before or during use. This step provides a use solution from the detergent composition.

[0106] In some embodiments for the use of the composition in a dishwashing process, the composition may be housed in a dispenser to provide a use dilution for use in a dishwashing machine (or other point of use). In one embodiment, a dispenser may be used to spray water (e.g., in a spray pattern from a nozzle) to form a use solution. For example, water may be sprayed towards a device having a solid composition or other holding reservoir, in which case the water reacts to form a diluted use solution. In an aspect, the use solution may be dispensed into the wash solution of a dishwashing machine.

[0107] The composition or its use solution can be contacted with a surface or article by a number of methods for applying the composition, such as spraying the composition, immersing the object in the composition, or combinations thereof. The concentrate or use concentration of the composition can be applied to or contacted with the article by any conventional method or device for applying a cleaning composition to an object. For example, the object can be wiped with the composition or a use solution made from the composition, sprayed with it, and / or immersed therein. The composition can be sprayed onto or wiped on a surface. That is, the composition can be poured onto a surface or the surface can be immersed in the composition. The contacting can be done manually or mechanically. Preferred embodiments contact the use solution of the solid composition within a dishwashing machine.

[0108] In embodiments, the use solution of the detergent composition has a pH of from about 11 to 13, from about 11.5 to 13, or from about 11 to 12, or from about 11.5 to 12. In some embodiments, the use solution has a pH of at least about 11 or at least about 11.5.

[0109] The method of using the detergent composition advantageously reduces the formation, precipitation, and / or deposition of scaling, including hard water scale such as calcium carbonate, on the hard surface contacted by the detergent composition. In embodiments, the detergent composition is employed to prevent the formation, precipitation, and / or deposition of hard water scale on hard surfaces and articles such as glass, dishes, silverware, etc. The detergent composition advantageously provides such prevention of the formation, precipitation, and / or deposition of hard water scale despite the high alkalinity of the detergent composition use solution in the presence of hard water. The detergent composition is effective in preventing the accumulation of hard water scale and / or the redeposition of dirt in various warewashing applications using water sources containing hard water. Additionally, the detergent composition is suitable for use in the temperature ranges typically used in industrial warewashing applications, including, for example, from about 150°F to about 165°F during the washing step and from about 170°F to about 185°F during the rinsing step.

[0110] In embodiments, the use solution of the detergent composition applied to the surface in need of treatment can contain a scale prevention component including a scale-inhibiting organic phosphonate and an additional scale inhibitor in an amount of at least about 5 ppm to about 1,500 ppm, about 5 ppm to about 1,000 ppm, about 10 ppm to about 1,000 ppm, or about 20 ppm to about 1,000 ppm.

[0111] Exemplary articles for treatment with the compositions disclosed herein are those in the warewashing industry, including articles such as metal products, plastic products, tableware, cups, glasses, silverware, and cooking utensils. For the purposes of the present invention, the terms "dish" and "ware" are used in the broadest sense to refer to a variety of articles used in the preparation, serving, consumption, and disposal of food, including pots, pans, trays, pitchers, bowls, plates, saucers, cups, glasses, forks, knives, spoons, spatulas, and other glass, metal, ceramic, plastic composite articles that are generally available for commercial or household kitchen or dining room use. Generally, these types of articles have surfaces provided for contact with food and / or beverage and can thus be referred to as food or beverage contact articles.

Examples

[0112] Examples

[0113] Embodiments of the present disclosure are further defined in the following non-limiting examples. While these examples illustrate certain embodiments of the present disclosure, it should be understood that they are provided by way of illustration only. From the foregoing discussion and these examples, one of ordinary skill in the art can identify the essential features of the present disclosure and make various changes and modifications to the embodiments of the present disclosure without departing from the spirit and scope thereof and adapt them to various uses and conditions. Accordingly, various modifications to the embodiments of the present disclosure will be apparent to one of ordinary skill in the art from the foregoing description in addition to those shown and described herein. Such modifications are also intended to be within the scope of the appended claims.

[0114] Example 1 Calcium carbonate precipitates from water with calcium hardness and alkalinity when these ions exceed the normal solubility limit of calcium carbonate. As the pH of the water increases, the driving force for calcium carbonate precipitation increases. Water that is stable at pH 8.0 can immediately precipitate calcium carbonate when the pH rises to 9.0. The anti-scaling efficacy of the liquid rinse aid compositions shown in Table 3 was evaluated. Using an alkaline detergent composition, scale inhibitor packages were compared, and a single scale inhibitor (phosphonate / polycarboxylate) was compared with their combinations to evaluate the efficiency of scale removal according to the inhibition percentage.

[0115] After mixing equal volumes of preheated (60 °C) hardness and alkali solutions, the test solution is stored at 60 °C for 48 hours. At the end of the incubation time, soluble calcium is measured using calcium titration, and the inhibition rate is calculated from the titration volume as a measure of the effectiveness of the inhibitor.

[0116] Test method:

[0117] Rinse all flasks with dilute HCl (3:1 distilled deionized water - concentrated HCl) and thoroughly rinse with deionized water before use. Any flask with discoloration, excessive scratching, or particle adhesion that remains after removal by acid should be discarded.

[0118] Solution to be heated:

[0119] Alkali solution: Add 96 grams of distilled deionized water minus the inhibitor volume to a clean 250 mL Erlenmeyer flask. Add the inhibitor volume (1 mL = 1 mg / L), cap or stopper the flask, and place it in an oven or water bath controlled at 60 °C.

[0120] Calcium solution: Add 95 grams of distilled deionized water to a 250 mL Erlenmeyer flask, followed by 5 mL of the calcium stock solution. Cap or stopper the flask and place it in an oven or water bath controlled at 60 °C.

[0121] Equilibrate all flasks to 60 °C (water bath - ~20 minutes; oven - ~1 hour 15 minutes).

[0122] Preparation of test solution:

[0123] Alkali addition: Add 4 mL of the alkali stock solution to the alkali flask after removing it from the temperature source.

[0124] Solution mixing: Add the alkali and calcium solutions to a 500 mL Erlenmeyer flask by simultaneously pouring both solutions from the funnels. Record the pH and return the stoppered or capped flask to the 60 °C temperature source for 5 hours.

[0125] After the 5-hour equilibration period, remove the flask from the bath or oven. Immediately record the final pH. Examine the appearance of the flask and record what type of scale might have formed. Typical findings include the following.

[0126] - Scale adhered to the sides of the flask.

[0127] - Scale particles settled to the bottom of the flask.

[0128] - Fluffy, non-adherent scale particles.

[0129] - Colloidal scale indicated by a blue cast in the solution.

[0130] Titration: Filter at least 10 g of the test solution through a 0.2 μm membrane filter. Dilute 10 g of the filtered sample to a total volume of 50 mL with distilled deionized water. Titrate the sample using Calgon Field Test No. 35-182-G for calcium measurement or Calgon Field Test No. 35-183-H for total hardness measurement. Prepare a calcium standard by diluting 10 mL of the calcium stock solution to 500 mL with distilled deionized water. Analyze the calcium as described in the previous step.

[0131] Calculate the inhibition percentage from the following formula. Inhibition % = V E - V o × 100 {V T - V o} In the formula, V E = The volume of titrant liquid (mL) required for the treated test sample V o = The volume of titrant liquid (mL) required for the untreated (blank) test sample V T = The volume of titrant liquid (mL) required for the calcium reference sample

[0132] The inhibition rate (%) of calcium carbonate scale was evaluated for the single components shown in Table 2 and for the combination of scale-inhibiting organic phosphonate (PAPEMP) and polycarboxylic acid (PAA / PMA).

[0133]

Table 3

[0134]

Table 4

[0135] The results are shown in Figure 1 and Tables 2 - 3. The results show that 20 ppm of PAPEMP + 20 ppm of PAA / PMA provides at least substantially the same anti-scaling effect as 40 ppm of PAPEMP alone. Similarly, 20 ppm of PAPEMP has better performance than 40 ppm of PAA. PMA, PAPEMP, and PAA all reach maximum efficacy at approximately 20 ppm, but the combination of components can be enhanced with a combination of components of approximately 1:1 (or 1:1:1).

[0136] Example 2 The anti-scaling effect of the detergent composition was evaluated using glassware in a commercially available dishwashing machine. Scale inhibitor packages were compared, and a single scale inhibitor (phosphonate / chelating agent / polycarboxylate) was compared with their combinations to evaluate the efficiency of scale removal according to the inhibition percentage.

[0137] Before the experiment, the dishwashing machine was prepared as follows. Turn on the power of the dishwashing machine, fill it with water, set the desired water temperature, and then add a delimer (Strip Away or Lime A Way 0.5 - 1L, wash 3 cycles). Next, turn off the power of the dishwashing machine, drain all the water in the washing tank, and check whether the scale has been completely removed. Rinse the dishwashing machine with tap water (rinse off the residual acid and foam). Prepare the compositions (detergent and rinse aid) to be used in the experiment.

[0138] Turn on the power of the dishwashing machine, fill it with water, and leave the overflow pipe open for about 2 minutes (drain the water in the rinse cylinder). After 2 minutes, tightly plug the overflow pipe, adjust the chemical concentration, and start filling with water. After placing the dishwashing machine in place, wash it for 2 - 3 cycles and test the water hardness, chemical concentration, and volume.

[0139] Experimental method: Seven glasses and ten stainless steel test pieces were placed in the dishwashing machine (weigh the test pieces and tie them around the rack). Place the seven glasses on the rack from end to end of the dishwashing machine for 100 cycles. After 100 cycles were completed, remove the rack from the dishwashing machine.

[0140] Regarding water hardness: Take 5 mL of water from the washing tank into a 5 mL tube, add an appropriate amount of indicator (Eriochrome Black T), and after the indicator is completely dissolved, if the color of the solution changes to pink, add 0.02N EDTA dropwise until the color of the solution turns blue, indicating that the titration end point has been reached. Half of the number of drops is the water hardness (gpg).

[0141] The evaluated detergents are shown in Table 4 compared to a base or benchmark formulation that provides PBTC and PAA / PMA (completely free of PAPEMP).

[0142]

Table 5

[0143]

Table 6

[0144] The results in Table 5 show the scaling rate, which is the weight gain / exposed surface area of the test piece (i.e., scale accumulation). The results are also shown in Figures 2A - 2C. Figure 2A shows the glass after 100 cycles using the reference formulation. Figure 2B shows the glass after 100 cycles using Formulation 1 where scale accumulation was significantly reduced compared to the benchmark. Figure 2C shows the glass after 100 cycles using Formulation 2 where scale accumulation was significantly reduced compared to the benchmark.

[0145] The results also included an evaluation of the scale inhibition rate on the steel test piece. This was calculated by comparing the inhibition rate against sodium hydroxide alone in a dishwasher without a scale inhibitor (9 drops of 250 ppm NaOH). The results are shown in Table 6.

[0146]

Table 7

[0147] The invention has been described in conjunction with its detailed description, but it should be understood that the foregoing description is intended to be illustrative and not to limit the scope of the invention, which is defined by the scope of the appended claims. Other embodiments, advantages, and modifications are within the scope of the following claims. Any reference to the accompanying drawings, which form a part of this specification, is shown by way of example only. It is understood that other embodiments may be utilized and structural changes may be made without departing from the scope of the present disclosure. All publications mentioned and / or referenced herein are hereby incorporated by reference in their entirety.

[0148] In certain forms, or from the perspective of means for performing the disclosed functions, or methods or processes for achieving the disclosed results, the foregoing description, or the following claims, or the features disclosed in the accompanying drawings, may be utilized, as appropriate, separately or in any combination of such features, to implement the invention in its various forms.

Claims

1. A detergent composition comprising: The following structure: 【Chemical 1】 (In the formula, Y is [Chemical 2] or a salt thereof, Y' is absent or 【Chemical Formula 3】 or a salt thereof, X is N, O, or OH, R １ and R ２ are each, independently, a linear or branched C1-C10 alkyl group, R ３ is -N(Y) ２ and n is from 1 to 20), a scale-inhibiting organic phosphonate having one of them, An additional scale inhibitor comprising at least one polycarboxylate, polycarboxylic acid, or a salt thereof, An alkali source comprising an alkali metal hydroxide, Water, A detergent composition comprising the above.

2. The solid composition comprises about 1 wt% to about 30 wt% of the scale-inhibiting organic phosphonate, about 0 wt% to about 20 wt% of the additional scale inhibitor comprising at least one polycarboxylate, polycarboxylic acid, or a salt thereof, about 10 wt% to about 90 wt% of the alkali source, and about 1 wt% to about 30 wt% of the water. The liquid composition comprises about 1 wt% to about 30 wt% of the scale-inhibiting organic phosphonate, about 0 wt% to about 20 wt% of the additional scale inhibitor comprising at least one polycarboxylate, polycarboxylic acid, or a salt thereof, about 5 wt% to about 80 wt% of the alkali source, and about 30 wt% to about 90 wt% of the water. The composition according to Claim 1.

3. The scale-inhibiting organic phosphonate constitutes about 1 wt% to about 10 wt% of the composition, the additional scale inhibitor comprising at least one polycarboxylate, polycarboxylic acid, or a salt thereof constitutes about 1 wt% to about 10 wt% of the composition, and the alkali source constitutes about 15 wt% to about 90 wt% of the composition. The composition according to Claim 1.

4. The salt of Y or Y' is a cation, preferably sodium or potassium. The composition according to any one of Claims 1 to 3.

5. The organic phosphonate has the structure: 【Chemical Formula 4】 (wherein Z is independently H or CH ３ and n is from 2 to 12) The composition according to any one of Claims 1 to 4.

6. The organic phosphonate has the structure: [Chemical Formula 5] The composition according to Claim 5.

7. The organic phosphonate has one of the following structures: 【Chemical Formula 6】 The composition according to any one of Claims 1 to 4.

8. The organic phosphonate has one of the following structures: [Chemical Formula 7] The composition according to any one of Claims 1 to 4.

9. The composition according to any one of claims 1 to 8, wherein the polycarboxylate, the polycarboxylic acid, or a salt thereof includes a homopolymer, copolymer, or terpolymer of polyacrylate, polymethacrylate, and / or polymaleate.

10. The composition according to claim 9, wherein the polycarboxylate, the polycarboxylic acid, or a salt thereof is a polyacrylic acid polymer and / or a polyacrylic acid / polymaleic acid polymer.

11. The composition according to any one of claims 1 to 10, wherein the alkali source further includes a second alkali source containing an alkali metal carbonate.

12. The composition according to any one of claims 1 to 11, further including at least one additional functional component including a builder and / or an enzyme.

13. The composition according to any one of claims 1 to 12, wherein the composition is a liquid, or a compressed or cast solid.

14. A method of using a detergent composition, the method comprising: providing a detergent composition according to any one of claims 1 to 13; contacting the detergent composition with water to form a use solution; contacting the use solution with a surface requiring cleaning and scale prevention; and the method includes the above steps.

15. The method according to claim 14, wherein the use solution has a pH of at least about 11 or at least about 11.

5.

16. The method according to claim 14 or 15, wherein the use solution is dispensed into a cleaning solution of a warewashing machine.

17. The method according to claim 16, wherein the warewashing machine is a commercial dishwashing machine, an on-site dishwashing machine, or a consumer dishwashing machine.

18. The method according to any one of claims 14 to 17, wherein the surface is an article including wares.

19. The method according to any one of claims 14 to 18, wherein the surface is a hard surface including metal, glass, or plastic.

20. The method according to any one of claims 14 to 19, wherein the use solution has a concentration of the scale-inhibiting organic phosphonate and the additional scale inhibitor of about 5 ppm to about 1,500 ppm, about 10 ppm to about 1,000 ppm, or about 20 ppm to about 1,000 ppm.

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